CN101208367B

CN101208367B - Self-crosslinking PU dispersions

Info

Publication number: CN101208367B
Application number: CN200680023125XA
Authority: CN
Inventors: J·马赞克; D·格利茨塔-弗郎茨; S·多尔; J·迈克斯纳; R·哈尔帕普; 海姆特·穆勒; O·弗莱克; 海诺·穆勒
Original assignee: Bayer MaterialScience AG
Current assignee: Covestro Deutschland AG; Bayer Intellectual Property GmbH
Priority date: 2005-06-29
Filing date: 2006-06-20
Publication date: 2011-05-18
Anticipated expiration: 2026-06-20
Also published as: JP5409003B2; PL1910437T3; ATE465191T1; ES2343079T3; BRPI0612815A2; KR20080039388A; US20070004856A1; DE502006006806D1; JP2008545023A; DE102005030225A1; KR101356293B1; CN101208367A; EP1910437A1; WO2007000262A1; EP1910437B1

Abstract

The invention relates to a method for producing self-crosslinking PU dispersions, and also to the use thereof.

Description

Self-crosslinking polyurethane PU dispersions

The present invention relates to prepare the method for self-crosslinking polyurethane PU dispersions, and also relate to their purposes.

In recent years, strict day by day along with what the discharging of release solvent management in the paint application was instructed, to the also obviously raising of requirement of water-borne coatings.Though existing operational water-based application system in a lot of Application Areass at present, these systems usually can not obtain the such high-quality level of conventional solvent base (solvent-borne) coating at aspect solvent resistance and the chemical resistant properties or other elasticity and mechanical endurance aspect.Particularly disclosing as yet so far can be by any polyurethane-based paints of water processing acquisition, and this material goes far towards to satisfy the strict demand in automotive OEM facing (the automotive OEM finishing) field.

This evaluation both had been applicable to the DE-A 4001783 that relates to specific anion modified aliphatic polyisocyanate, also be applicable to the system among DE-A 2456469, DE-A 2814815, EP-A 0012348 and the EP-A 0424697, they have described the water-based porcelain tackiness agent based on blocked polyisocyanates and organic polyhydroxy compound.In addition, can not be used for (realization) described purpose to a great extent based on end capped water-soluble carbamate prepolymer among system that contains carboxyl polyurethane prepolymer and blocked isocyanate base or the DE-A 3234590 (they have high functionality, so the utmost point is unsuitable for preparing elastic coating) among the DE-A 2708611.

Used single component (1K) porcelain has been carried out further improvement in recent years, for example in EP-A 0576952, described water-soluble or water dispersible polyol and combination water-soluble or the water dispersible blocked polyisocyanates, or the combination that in DE-A 19930555, has disclosed water dispersible hydroxyl-functional binder ingredients, aminoresin and other component of amido-containing acid ester base, wherein said binder ingredients contains end capped isocyanate group and makes by the multistage process.EP-A 0427028 has described the water-dispersible adhesive combination as oven dry two road topcoatings (surfacer), its by urethane-modified vibrin (containing carboxylic acid ester groups), add aminoresin in this dispersion and/or blocked polyisocyanates and suitably under the situation extra emulsifying agent constitute.The end-capping reagent that is exclusively used in polyisocyanates is alcohol, phenol, lactan and oxime.The shortcoming of these one-component systems is: previously prepared component is mixed with coating subsequently, must carry out extra mixing step thus.

U.S. Patent application WO 02/14395 has described self-crosslinkable polyurethane dispersions, and it comprises: the polyvalent alcohol of amido-containing acid ester base and hydroxyl, and it produces by statistics blending hydrophilizing agent (hydrophilicizing agent); The polyisocyanates of non-hydrophily, its with dimethyl pyrazole piperidine derivatives end-blocking at least 50 equivalent %.

Yet coating described in the prior can not satisfy all requirements of professional, especially about the requirement of solids content.

An object of the present invention is to provide the 1K baking system of improvement, wherein this coating should specifically have high solids content, and coating should have good solvent resistance.

Found a kind of method, this method can make self-crosslinkable polyurethane dispersions to be prepared have the solids content of improvement, and makes by its coating that makes and have significant good solvent resistance.

The present invention provides a kind of method that is used to prepare self-crosslinkable polyurethane dispersions thus, a1 in the method) and a2) reaction make NCO-official can or optional OH-functional prepolymer, then this prepolymer again with a3) and optional a4) reaction makes the urethane that OH-official can and not contain NCO-(NCO-free), wherein

A1) be polyisocyanates,

A2) be at least a polyol component, its average OH functionality 〉=2, number-average molecular weight is 62～2500g/mol, also has at least a acid-functionalized compound,

A3) be at least a other polyol component, its number average OH functionality＞1,

A4) randomly be other polyisocyanate component, its can with a1) identical or different,

Component a1)～a4) complete reaction was carried out before or after adding blocked polyisocyanates, maybe this carries out before or after being added on any composition step, or at component a1)～after a4) reaction takes place, make this end capped polyisocyanates by polyisocyanates and end-capping reagent in position

At last, make a5 by adding neutralizing agent) deprotonation wholly or in part,

A5) be the acid groups of resulting composition,

And gained urethane is scattered in the water.

The present invention also provides by the dispersion of method preparation of the present invention and the polyether polyols with reduced unsaturation that contains this dispersion.

In being considered as whole method of the present invention, isocyanate group (comprising capping group) elects 0.5～5.0 as with the ratio of all isocyanate reacting groups: 1, preferred 0.6～2.0: 1, more preferably 0.8～1.5: 1.

At component a1) and a4) in, may use all to contain all organic compound of isocyanate group, but the aliphatic series of preferred NCO functionality 〉=2, alicyclic, aromatics or heterocycle polyisocyanates, it can use separately or use with any required form of mixtures each other, as for these compounds be by phosgenation processes or by no phosgene method make then unimportant.

The example of this type of polyisocyanates is: tetramethylene diisocyanate, 1,3-and 1,4-hexamethylene vulcabond, 1, hexamethylene-diisocyanate (HDI), 1-isocyanate group-3,3,5-trimethylammonium-5-methylcyclohexane isocyanic ester (isophorone diisocyanate, IPDI), methylene radical-two (4-isocyanato-hexanaphthene) (methylene-bis-(4-isocyanatocyclohexane)), tetramethyl xylylene diisocyanate (TMXDI), three isocyanato-nonanes, tolylene diisocyanate (TDI), ditan 2,4`-and/or 4,4`-vulcabond (MDI), triphenyl methane 4,4-vulcabond or naphthylidene 1,5-vulcabond, and any desired mixt of this kind isocyanate.

Equally very suitable is derived from following structure or polyisocyanates with following structure: urea diketone, carbodiimide, isocyanuric acid ester, iminooxadiazinedionepolyisocyanates diketone, biuret, carbamate, allophanate, oxadiazine triketone or acylurea; and the polyisocyanate prepolymers of number average NCO functionality＞1, they are to obtain by the organic materials reaction that a kind of and per molecule in the above-mentioned polyisocyanates that makes molar excess at first contains at least 2 isocyanate reactive hydrogen atoms (for example existing with the OH form).

At a1) in, the preferred compound that uses the above-mentioned type with 140～1000g/mol molecular weight.

At component a1) and/or a4) in particularly preferably contain described type polyisocyanates or the polyisocyanate mixtures that only carries out the aliphatic series or the isocyanate group of alicyclic connection, especially based on 1, hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI) and/or dicyclohexyl methyl hydride 4,4 '-diisocyanate based (4,4 '-diisocyanatodicyclohexylmethane).

Polyol component a2) preferred average OH functionality is 2～6, number-average molecular weight is 62～2500g/mol, preferred 62～1000g/mol, more preferably 62～500g/mol, and contain acid-functionalized compound, this compound also contains at least one isocyanate-reactive group except acid functional group, for example OH, NH or SH.

Preferred ingredient a2) satisfies above-mentioned definition, and comprise 1,4-butyleneglycol, 1,3 butylene glycol, 1,6-hexylene glycol, 2,2,4-trimethylammonium-1, the pure and mild polyether glycol of the polyester polyols of 3-pentanediol, TriMethylolPropane(TMP) and/or number-average molecular weight≤2000g/mol.Using under the situation of polyethers, in component a2) total amount be benchmark, component a2) preferably contain acid-functionalized compound more than 50mol%, this compound except sour official can, also contain at least one isocyanate-reactive group, for example OH, NH or SH.

The example of this type of acid-functionalized compound is: hydroxyl functional carboxylic acid and/or sulfonic acid, preferred list-and dihydroxy carboxylic acids, for example 2-oxyacetic acid, 3-hydroxy-propionic acid, 12-hydroxyl-9-stearic acid (ricinolic acid), hydroxypivalic acid, lactic acid and/or dimethylol propionic acid.Preferred hydroxypivalic acid, lactic acid and/or dimethylol propionic acid, particularly preferred dimethylol propionic acid.

Particularly preferably a2) only contain above-mentioned acid-functionalized compound; Particularly preferably be and only use dimethylol propionic acid) as a2.

At a3) in used polyol component comprise:

B1) binary～hexavalent alcohol, its number-average molecular weight are 62～300g/mol, preferred 62～182g/mol, and more preferably 62～118g/mol,

B2) polyvalent alcohol, its OH functionality 〉=2, and number-average molecular weight is 300～5000g/mol, preferred 300～3000g/mol, more preferably 300～2000g/mol and/or

B3) simple function linear polyether, its number-average molecular weight are 300～3000g/mol, preferred 300～2000g/mol, more preferably 300～1000g/mol.

The polyvalent alcohol b1 that is fit to) comprises the binary～hexavalent alcohol that do not contain ester group and/or their mixture.Representational example is an ethylene glycol, 1,2-and 1, ammediol, 1,4-or 1,2-butyleneglycol or 1,6-hexylene glycol, 1,4-dihydroxyl hexanaphthene, glycerol, trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane and sorbyl alcohol.With regard to components b 1) with regard to, it also can adopt certainly has the alcohol that radical ion maybe can be converted into the group of radical ion.

Be preferably used as b1) compound be 1,4-or 1,3 butylene glycol, 1,6-hexylene glycol and/or TriMethylolPropane(TMP).

Components b 2) suitable polyvalent alcohol is selected from: polyethers, polyester and/or polycarbonate.B2) preferably include at least a polyvalent alcohol, this polyvalent alcohol comprises ester group, and number-average molecular weight is 350～4000g/mol, preferred 350～2000g/mol, more preferably 350～1000g/mol.Preferred average OH functionality is 2～4 OH base/molecules.

Known this type of polyvalent alcohol that contains ester group own is a polyester polyol, and they are from low molecular weight polyols and dicarboxylic acid synthetic.The example of suitable low molecular weight polyols for this purpose comprises: 1, and 4-butyleneglycol, 1,3 butylene glycol, 1,6-hexylene glycol, 2,2,4-trimethylammonium-1,3-pentanediol, TriMethylolPropane(TMP), tetramethylolmethane or sorbyl alcohol.The example of the dicarboxylic acid that is fit to comprises: aromatic dicarboxylic acid, for example phthalic acid, m-phthalic acid and terephthalic acid; Alicyclic dicarboxylic acid, for example hexahydrophthalic acid, tetrahydrochysene phthalic acid, interior methyne tetrahydrochysene phthalic acid and/or their acid anhydrides; And aliphatic dicarboxylic acid, for example succsinic acid, pentanedioic acid, hexanodioic acid, cork acid, nonane diacid, sebacic acid and/or their acid anhydrides.The preferred aliphatic dicarboxylic acid that adopts synthesizes esterdiol.

With regard to components b 2) polyester polyol with regard to, preferably using number-average molecular weight is 350～4000g/mol, preferred 350～2000g/mol, the more preferably pcl-diol acid lactone of 350～1000g/mol.By glycol, triol or the glycol of exemplary types/three alcohol mixtures above is that initiator can obtain these compounds by conventional methods with 6-caprolactone.

Preferred pcl-diol acid lactone is with 1, and the 6-hexylene glycol is that initiator prepares by the polymerization 6-caprolactone.

Particularly the preferred polyester polyvalent alcohol is based on those of hexanodioic acid, phthalic acid, m-phthalic acid and tetrahydrochysene phthalic acid.

In components b 2) in also can use (being total to) polyethers of oxyethane, propylene oxide and/or tetrahydrofuran.Preferred number average molecular weight is the polyethers of 500～2000g/mol, for example polyethylene oxide or polyoxy heterocycle pentane diol.

In addition, b2) also can comprise the polycarbonate of hydroxyl, for example poly-carbonic acid 1,6-hexylene glycol ester or polyestercarbonate, its preferred number-average molecular weight is 400～4000g/mol, more preferably 400～2000g/mol.

The example of the simple function linear polyether that is fit to components b 3) is oxyethane and/or propylene oxide (being total to) polyethers.Preferably by the polyalkylene oxide base polyethers of the initial preparation of monohydroxy-alcohol, its number-average molecular weight is 350～2500g/mol, and comprises at least 70% ethylene oxide unit.Particularly preferably having more than 75% ethylene oxide unit and number-average molecular weight is 300～2500g/mol, (being total to) polymkeric substance of preferred 500～1000g/mol.Be used to prepare the monofunctional alcohol of the preferred 1-6 of a starting molecule carbon atom of these polyethers.

Except that component a1)～a4) used polyisocyanates (existing) no matter whether they are the end-blocking form corresponding to and/or based on being defined in a1 respectively) and a4) in compound.

Polyisocyanates used herein also can comprise hydrophilic radical extraly.The hydrophilizing agent that can the blending form exists is all positively charged ions, negatively charged ion and/or the non-ionic compound that is suitable for these purposes.They are for example single-and/or dihydroxy carboxylic acids or monofunctional alkyl ethoxylate (alkyl ethoxylate).Certainly also can adopt the mixture of different hydrophilic agent.Preferably dimethylol propionic acid and/or monofunctional alkyl ethoxylate.

Also can adopt the mixture of the polyisocyanates of hydrophily and non-hydrophily.Preferably use hydrophilizing agent to prepare stable blocked polyisocyanates dispersion with insufficient amount.Those skilled in the art can determine this tittle at an easy rate by the routine test method.

Used herein polyisocyanates is at component a1 with the end-blocking form)～a4) reaction is before or under the situation about only adding after described reaction, these blocked polyisocyanates have with this as the end capped NCO group of end-capping reagent well known by persons skilled in the art.

The example of suitable end-capping reagent is for example for example alkyl alanine ester, tert-butyl benzyl amine, dimethyl pyrazole, triazole and their mixture of methyl ethyl ketoxime, Diisopropylamine, ester amine of ε-Ji Neixianan, diethyl malonate, methyl aceto acetate, oxime.Preferably ε-Ji Neixianan, methyl ethyl ketoxime, Diisopropylamine, 3, triazole and/or their mixture.

The amount of free NCO group is less than 1 weight % usually in these blocked polyisocyanates, preferably is less than 0.1 weight %.

Also can be at a1)～a4) each other after the reaction, substitute the end capped polyisocyanates of used aforementioned type with polyisocyanates with free NCO group, carry out end-blocking then in position.The end-capping reagent that is fit to is with mentioned above identical.In this case, after their consumption makes that end capping finishes,, preferably exist with the end-blocking form more than free NCO group before 99% reaction usually more than 90%.

In order to quicken end capping, also can use catalyzer, for example: tertiary amine, tin compound, zn cpds or bismuth compound, especially triethylamine, 1,4-diazonium two ring [2.2.2] octane, two stannous octoates or two lauric acid, two uncle Ding Xi.

The known end capped optimum condition of original position that carries out of those skilled in the art.At end-capping reagent with will carry out to stir usually till the free isocyanic ester can not be detected again after end capped isocyanate component is added to together.Except using single end-capping reagent, also can adopt the mixture of two or more end-capping reagents to carry out end-blocking to carrying out end capped multiple polyisocyanates, the form that these polyisocyanates also can mixture under suitable situation exists.

Another kind of possibility is the free NCO group of part and end-capping reagent reaction that only makes vulcabond, then all not end capped NCO groups is reacted the polyisocyanates of formation urea diketone-(uretdione-), allophanate and/or biuret-modification.

If necessary, also can use solvent certainly in any time point in the inventive method process, described solvent (if suitable) is removed in follow-up preparation once more.In addition, also can adopt catalyzer, solubility promoter and other auxiliary agent and additive.

In the process of the inventive method, also can in reaction mixture, add a large amount of relatively (part) water-miscible solvents, for example acetone or methyl ethyl ketone.When reaction stops, in this reaction mixture, add entry, and desolvate by distilling to remove.This is also referred to as acetone or slurry method.The advantage of this technology is that the solvent composition in refining dispersion is lower.

Be used for a5) the example of neutralizing agent be: triethylamine, dianol, dimethylcyclohexylamine, trolamine, methyldiethanolamine, diisopropanolamine (DIPA), ethyl diisopropanolamine (DIPA), di-isopropyl hexahydroaniline, N-methylmorpholine, 2-amino-2-methyl-1-propanol, ammoniacal liquor or their any desired mixt.Preferred neutralizing agent is a tertiary amine, for example triethylamine, di-isopropyl hexahydroaniline and dimethylethanolamine, particularly preferably dimethylethanolamine.

Usually the amount of used neutralizing agent is calculated so that the degree of neutralization of carboxylic acid in the urethane of the present invention and/or sulfonic acid group (for the mol ratio of used amine and existing acidic-group) is at least 50%, preferred 80%～120%, more preferably 95%～105%.Neutralization reaction can be before dispersing or dissolving step, in or carry out afterwards.Yet preferably before adding water, carry out neutralization reaction.

Respectively independently processing step can all carry out in single reaction vessel, and perhaps each step then can be carried out in different reaction vessels and the gained intermediate is mixed for further reaction.

One preferred embodiment in, use before in being scattered in water: 5%～50%, preferred 8%～40%, the more preferably NCO-of 10%～30 weight % and/or OH-functional prepolymer; 0.1%～20%, preferred 1%～10%, the more preferably component a4 of 1%～5 weight %); 20%～90%, preferred 40%～80%, the more preferably component a3 of 50%～70 weight %); 2%～50%, preferred 5%～30%, more preferably 10%～25% end capped polyisocyanates; And 0.01%～10%, preferred 0.5%～5%, the more preferably component a5 of 1%～3 weight %).Described per-cent does not comprise water section based on described component, and their summation is 100%.

Another preferred embodiment in, 2%～40%, preferred 5%～30%, more preferably prepare 5%～50% in 10%～25% the end capped polyisocyanates, preferred 10%～40%, the more preferably NCO-of 10%～30 weight % and/or OH-functional prepolymer, and before in being scattered in water, with this prepolymer and 0.1%～20%, preferred 1%～10%, the more preferably component a4 of 1%～5 weight %), 30%～90%, preferred 40%～80%, the more preferably component a3 of 50%～70 weight %) and 0.01%～10%, preferred 0.5%～5%, the more preferably component a5 of 1%～3 weight %) mix.Described per-cent does not comprise water section based on described component, and their summation is 100%.

Another equally preferred embodiment in, make 5%～50%, preferred 10%～40%, the more preferably NCO-of 10%～30 weight % and/or OH-functional prepolymer and 0.1%～20%, preferred 1%～10%, the more preferably component a4 of 1%～5 weight %), 30%～90%, preferred 40%～80%, the more preferably component a3 of 50%～70 weight %) reaction, end-capping reagent and other isocyanic ester of adding a certain amount of (amounts of) then, thereby produced 2%～40% by back two kinds of components, preferred 5%～30%, more preferably 10%～25% blocked polyisocyanates.At last, in being scattered in water before, this mixture and 0.01%～10% is preferred 0.5%～5%, the more preferably component a5 of 1%～3 weight %) mix.Described per-cent does not comprise water section based on described component, and their summation is 100%.

The solids content that dispersion had that obtains with this method of the present invention is generally 30%～60 weight %, preferred 40%～50 weight %.

The dispersion that obtains with the inventive method can be used as the baked single-component system that contains free hydroxyl group, is used for the preparation of varnish, paint and other preparation.In these are used, also can use auxiliary material and additive habitual in the paint-on technique field, for example pigment, flow control agent, prevent to bubble or the additive or the catalyzer of bubbling.

The present invention also provides the purposes of this dispersion in preparation paint, varnish or tackiness agent, in particular for the automotive OEM facing, its can also (be used for) coating and coiled material continuous coated.

Can adopt any required method in the paint-on technique, for example spray, be coated with, dipping, overflow or use cylinder, doctor, with these water-based mono-component coating with any required resistant substrates of one or more layers paint.This dried thickness of filming is generally 0.001～0.3mm.

The example of the base material that is fit to is: metal, plastics, timber or glass.This is filmed at 80～260 ℃, and preferred 130～260 ℃ solidify down.

This water-based mono-component coating preferably is applicable to coating and the japanning system that produces on the steel disc, for example is used to produce car body, machine, panel board, drum or container.Particularly preferably they are at preparation car surface coating and/or finish paint material.

Embodiment:

Desmodur 44M: monomer ditan 4,4 '-vulcabond, isocyanate content are 34 weight %, Bayer Materialscience AG (Bayer MaterialScience AG), Leverkusen Germany

Desmodur VL R 20: based on the aromatic polyisocyanate of diphenylmethanediisocyanate, isocyanate content is 31.5 weight %, Bayer Materialscience AG, Leverkusen Germany

Pluriol A 500E: poly glycol monomethyl ether, molecular weight are 500g/mol, BASF, Ludwigshafen, Germany

Desmodur Z 4470 M/X: based on the aliphatic polyisocyanate of isophorone diisocyanate, the solution of 70 weight % concentration in the mixture of acetate methoxyl group propyl ester and dimethylbenzene (1/1), isocyanate content is 12 weight %, Bayer Materialscience AG, Leverkusen Germany

Desmodur Z 4470: based on the aliphatic polyisocyanate of isophorone diisocyanate, isocyanate content is 17 weight %, Bayer Materialscience AG, Leverkusen Germany

Desmodur VP LS 2253: based on the end-blocking aliphatic polyisocyanate of hexamethyl vulcabond, isocyanate content is 11 weight % (end capped), Bayer Materialscience AG, Leverkusen Germany

Shellsol SN 100: aromatic hydrocarbons mixture, boiling range are 160～180 ℃, shell stock company (Shell AG)

Except as otherwise noted, all per-cents all are weight percentage.

The viscosity of being reported is measured down at 23 ℃ according to DIN 530 19 by rotational viscometry, and used selection viscometer is available from pacifying with handkerchief Germany stock Co., Ltd (Anton Paar Germany GmbH, Ostfildern,Germany).

Except as otherwise noted, according to DIN-EN ISO 11909, stereometry NCO content.

The particle diameter of being reported is measured (instrument: Ma Erwen ζ sizer 1000 (Malvern Zeta sizer 1000), Ma Erwen Instr Ltd. (Malvern Inst.Limited)) by the laser correlation spectrometry.

(bands of a spectrum are 2260cm to adopt the IR spectrography ^-1) the free NCO group of detection.

Embodiment 1

Dropwise mix with the 1-butanols of 37.1g with the Desmodur 44M that stirs 468.8g under 80 ℃.Add catalyzer (0.05g (2 ethyl hexanoic acid) after 1 hour ₂Zinc, 50%, in MPA), this batch of material is stirred more than 12 hours down at 80 ℃, NCO content drops to about 21.8% (being 22.8% in theory) during this period.Subsequently, provide 497g N-Methyl pyrrolidone, and with the batch of material cool to room temperature.The methyl ethyl ketoxime that dropwise adds 239.3g then, its speed make and by thermopositive reaction the temperature of this batch of material to be risen to about 70 ℃.Then it is stirred down at 70 ℃, until no longer be measured to free NCO group (about 1 hour) by the IR spectrography.Obtain lurid liquid thus, its solids content is 60%, and viscosity is 7000mPas, even if its go through the several months can crystallization yet.

Embodiment 2

Be dissolved in the 146g N-Methyl pyrrolidone by the Desmodur VL R 20 that stirs 132g under the room temperature.Under 50 ℃, dropwise this homogenizing mixture is mixed with the methyl ethyl ketoxime of 87g then, its speed makes and by thermopositive reaction the temperature of this batch of material to be risen to about 80 ℃.Then it is stirred down at 80 ℃, until no longer be measured to free NCO group (about 1 hour) by the IR spectrography.Obtain the liquid of brown thus, its solids content is 60%, and viscosity is 1320mPas, and it is gone through more than 1 year and still to keep stable and crystallization can not take place.

Embodiment 3

Under 80 ℃, be dissolved in the 150g N-Methyl pyrrolidone by the Desmodur VL R 20 that stirs 132g.Under 80 ℃, dropwise this homogenizing mixture is mixed with the 1-butanols of 9.9g.Add catalyzer (0.01g (2 ethyl hexanoic acid) after 1 hour ₂Zinc is 50%, in MPA), 80 ℃ of following restir 1 hour, NCO content dropped to about 10.4% (being 10.5% in theory) during this period with this batch of material.Subsequently, batch of material is cooled to 50 ℃, adds 3 of 83.5g, the 5-lutidine, its speed makes and by thermopositive reaction the temperature of this batch of material is risen to about 70 ℃.Then it is stirred down at 70 ℃, until no longer be measured to free NCO group (about 2 hours) by the IR spectrography.Obtain the liquid of brown thus, its solids content is 60%, and viscosity is 700mPas, and it is gone through and reaches 8 months and still keep stability in storage.

Embodiment 4

Stir down Desmodur VL R 20 addings of 132g are equipped with in the container of 13.2g Pluriol A 500E, this initial charge is heated to 80 ℃.Under 80 ℃ this homogenizing mixture is mixed with catalyzer (0.015g dibutyl tin laurate), stirred this batch of material 1 hour down at 80 ℃, NCO content drops to about 27.1% (being 28.2% in theory) during this period.Dilute this batch of material with the 151g N-Methyl pyrrolidone then, and be cooled to 50 ℃.Thereafter, dropwise add the 82g methyl ethyl ketoxime, its speed makes brings up to about 80 ℃ by thermopositive reaction with the temperature of this batch of material.Stir down at 80 ℃ then, until until no longer be measured to free NCO group (about 1 hour) by the IR spectrography.Obtain the liquid of brown thus, its solids content is 60%, and viscosity is 1200mPas, and it is gone through more than 1 year and still to keep stable and crystallization can not take place.

Embodiment 5

Be dissolved in the N-Methyl pyrrolidone of 584g by the Desmodur VL R 20 that stirs 503.2g under 80 ℃.Under 80 ℃, this homogenizing mixture is dropwise mixed with the 13.4g diethylene glycol monomethyl ether.After 1 hour, add catalyzer (0.04g (2 ethyl hexanoic acid) ₂Zinc is 50%, in MPA), 80 ℃ of following restir 1 hour, NCO content dropped to about 12.8% (being 13.5% in theory) during this period with this batch of material.Subsequently, batch of material is cooled to 30 ℃, dropwise adds the Diisopropylamine of 359.2g, its speed makes and by thermopositive reaction the temperature of this batch of material to be risen to about 70 ℃.Then it is stirred down at 80 ℃, until no longer be measured to free NCO group (about 1.5 hours) by the IR spectrography.Obtain the liquid of brown thus, its solids content is 60%, and viscosity is 2910mPas, and it is gone through still maintenance stability more than 1 year and crystallization can not take place.

Embodiment 6

Be dissolved in the acetate methoxyl group propyl ester of 303.7g by the Desmodur VL R 20 that stirs 316.8g under the room temperature.This homogenizing mixture is dropwise mixed with 352.64g N-benzyl-N-TERTIARY BUTYL AMINE, and its speed makes and by thermopositive reaction the temperature of this batch of material to be risen to about 50 ℃.Under 50 ℃, it is stirred then, keep constant until NCO content.Dropwise add other 19.59g N-benzyl-N-TERTIARY BUTYL AMINE then, under 50 ℃, stir this batch of material once more, keep constant until NCO content.At last, dropwise add 1.96g N-benzyl-N-TERTIARY BUTYL AMINE, stir this batch of material, until no longer be measured to isocyanate group (about 1 hour) by the IR spectrography.Obtain the liquid of brown thus, its solids content is 60%, and viscosity is 7500mPas.

Embodiment 7

Under 50 ℃, 95.41g (0.43mol) isophorone diisocyanate is mixed with the solution of 28.77g (0.215mol) dimethylol propionic acid in the 57.54g N-Methyl pyrrolidone, then with this mixture heating up to 80 ℃ and stirred 90 minutes.Its nco value subsequently is 9.33%.Stir and add 28.08g (0.078eqNCO) Desmodur Z 4470 M/X and 446.7g (1.4eq OH) polyester down, this polyester is by hexanodioic acid, different phthalic acid, TriMethylolPropane(TMP), neopentyl glycol and propylene glycol, its OH number is 189, and this mixture was stirred 90 minutes; Can not measure the NCO group again by the IR chromatography then.At 70 ℃ of embodiment 2 compounds that add 164.18g (1.73eq end-blocking NCO) down, carry out 10 minutes stirring then, measure 19.12g (0.215mol) dimethylethanolamine then, stirred subsequently 30 minutes.Under 70 ℃, this batch of material is dispersed in the 733.9g deionized water then, then down stirred 1 hour, and under agitation cooled off 4 hours at 50 ℃.Dispersions obtained have following character:

Solids content 41%

pH 6.97

Viscosity 2350mPas

Particle diameter (laser correlation spectrometry, LCS) 29nm

Embodiment 8

50 ℃ down by stirring, 114.68g (0.5015mol) isophorone diisocyanate is mixed with the solution of 38.92g (0.29mol) dimethylol propionic acid in the 93.07g N-Methyl pyrrolidone, with this mixture heating up to 50 ℃, stirred 3.5 hours down at 85 ℃.This moment, the NCO content of this reaction mixture was 7.42% (calculated value: 7.66%).Add 19.37g (0.085mol) isophorone diisocyanate then, (21.06g 0.06eq NCO) Desmodur Z 4470,335.0g (1.05eq OH) polyester is (by hexanodioic acid, different phthalic acid, TriMethylolPropane(TMP), neopentyl glycol and propylene glycol make, the OH number is 189), 323.70g (0.82eq OH) polyester is (by different phthalic acid, hexanodioic acid, 1, the 6-hexylene glycol, TriMethylolPropane(TMP) and Tetra hydro Phthalic anhydride make, the OH number is 254), and 77.4g (0.045mol) polyester is (by hexanodioic acid, 1,6-hexylene glycol and neopentyl glycol make, molar average weight is 1700), this mixture was stirred 2 hours down at 85 ℃.No longer record NCO group by the IR spectrography this moment.After this mixture is cooled to 70 ℃, add the compound of 123.14g (0.34eq end-blocking NCO) embodiment 2, stirred then 30 minutes, be cooled to 60 ℃, add 25.91g (0.29mol) dimethylethanolamine, restir 30 minutes.Add the 1102.4g temperature then and be 70 ℃ deionized water, then stirred these batch of materials 60 minutes, stir and let alone down to cool off at 60 ℃.Dispersions obtained have following character:

Solids content 45.4%

pH 7.72

Viscosity 4100mPas

Particle diameter (laser correlation spectrometry, LCS) 45nm

Embodiment 9

50 ℃ are mixed 147.90g (0.665mol) isophorone diisocyanate by stirring down with the solution of 50.30g (0.375mol) dimethylol propionic acid in the 100.60g N-Methyl pyrrolidone, with this mixture heating up to 85 ℃, and stirred 3.5 hours down at 85 ℃.This moment, the NCO content of this reaction mixture was 7.99% (calculated value: 8.15%).Add 4.45g (0.02mol) isophorone diisocyanate then, (21.06g 0.06eq NCO) Desmodur Z 4470 (Bayer Corp, Lai Wokusen), 335.0g (1.05eq OH) polyester is (by hexanodioic acid, different phthalic acid, TriMethylolPropane(TMP), neopentyl glycol and propylene glycol make, the OH number is 189), 323.70g (0.82eq OH) polyester is (by different phthalic acid, hexanodioic acid, 1, the 6-hexylene glycol, TriMethylolPropane(TMP) and Tetra hydro Phthalic anhydride make, the OH number is 254), and 77.4g (0.045mol) polyester is (by hexanodioic acid, 1,6-hexylene glycol and neopentyl glycol make, molar average weight is 1700), this mixture was stirred 2 hours down at 85 ℃.No longer record NCO group by the IR spectrography this moment.After this mixture is cooled to 70 ℃, add the compound of 252.80g (0.64eq end-blocking NCO) embodiment 2, stirred then 30 minutes, be cooled to 60 ℃, add 33.43g (0.375mol) dimethylethanolamine, restir 30 minutes.The deionized water that adds 70 ℃ of 1499.8g then then stirred this batch of material 60 minutes at 60 ℃, let alone cooling under stirring.Dispersions obtained have following character:

Solids content 39.9%

pH 7.85

Viscosity 200mPas

Particle diameter (laser correlation spectrometry, LCS) 41nm

Embodiment 10

Repeat embodiment 7 described methods, but with the compound of 179.40g Desmodur VP LS 2253 and 1027.8g water alternate embodiment 2.Dispersions obtained have following character:

Solids content 42%

pH 7.69

Viscosity 900mPas

Particle diameter (laser correlation spectrometry, LCS) 49nm

Embodiment 11

Repeat embodiment 7 described methods, but with the compound of the compound alternate embodiment 2 of 148.93g embodiment 1.Dispersions obtained have following character:

Solids content 42%

pH 7.80

Viscosity 1600mPas

Particle diameter (laser correlation spectrometry, LCS) 309nm

Embodiment 12

Repeat embodiment 7 described methods, but with the compound of the compound alternate embodiment 2 of 168.68g embodiment 3.Dispersions obtained have following character:

Solids content 45%

pH 7.54

Viscosity 4200mPas

Particle diameter (laser correlation spectrometry, LCS) 40nm

Embodiment 13

Repeat embodiment 7 described methods, but with the compound of the compound alternate embodiment 3 of 164.88g embodiment 4.Dispersions obtained have following character:

Solids content 45%

pH 7.85

Viscosity 1600mPas

Particle diameter (laser correlation spectrometry, LCS) 78nm

Embodiment 14

Under 50 ℃, the 95.41g isophorone diisocyanate is mixed with the solution of 30.18g dimethylol propionic acid in 52.58g acetate methoxyl group propyl ester and 7.78g N-Methyl pyrrolidone, with this mixture heating up to 80 ℃, stirred 90 minutes, keep constant until its nco value.Adding 12.64g Desmodur Z4470 M/X and 186.67g polyester (are made by hexanodioic acid, different phthalic acid, TriMethylolPropane(TMP), neopentyl glycol and propylene glycol under stirring, the OH number is 189), the 194.19g polyester is (by different phthalic acid, hexanodioic acid, 1,6-hexylene glycol, TriMethylolPropane(TMP) and Tetra hydro Phthalic anhydride make, the OH number is 254) and the 85.72g polyester (by hexanodioic acid, 1,6-hexylene glycol and neopentyl glycol make, molar average weight is 1700), this mixture was stirred 2 hours down at 85 ℃.No longer record NCO group by the IR spectrography this moment.Then, stirred 10 minutes, be metered into the 19.12g dimethylethanolamine then, stirred this mixture 30 minutes at 70 ℃ of compounds that add 178.3g embodiment 1 down.Then it is dispersed in the deionized water of 70 ℃ of 945g, stirred 1 hour down, stir cooling down 4 hours at 50 ℃.Dispersions obtained have following character:

Solids content 40%

pH 8.67

Viscosity 1350mPas

Particle diameter (laser correlation spectrometry, LCS) 60nm

Provided herein in blocked isocyanate 2 examples of the possibility of synthetic polymer system.It has only needs a reactor and can omit the advantage of the transfer in the fs.

Embodiment 15

(Bayer Corp Lai Wokusen) is dissolved in the 146g N-Methyl pyrrolidone with 132g Desmodur VL R 20 by stirring under the room temperature.Under 50 ℃ this homogenizing mixture is dropwise mixed with the 87g methyl ethyl ketoxime, its speed makes and by thermopositive reaction the temperature of this batch of material to be risen to about 80 ℃.Under 80 ℃, it is stirred then, until no longer be measured to free NCO group (about 1 hour) by the IR spectrography.Add 147.90g (0.665mol) isophorone diisocyanate then, and stirring adds the solution of 50.30g (0.375mol) dimethylol propionic acid in the 100.60g N-Methyl pyrrolidone under 50 ℃, with this mixture heating up to 85 ℃, stirred 3.5 hours down at 85 ℃.This moment, the NCO content of this reaction mixture was 4.43% (calculated value: 4.42%).Add 4.45g (0.02mol) isophorone diisocyanate then, (21.06g 0.06eq NCO) Desmodur Z 4470 (Bayer Corp, Lai Wokusen), 335.0g (1.05eq OH) polyester is (by hexanodioic acid, different phthalic acid, TriMethylolPropane(TMP), neopentyl glycol and propylene glycol make, the OH number is 189), 323.70g (0.82eq OH) polyester is (by different phthalic acid, hexanodioic acid, 1, the 6-hexylene glycol, TriMethylolPropane(TMP) and Tetra hydro Phthalic anhydride make, the OH number is 254), and 77.4g (0.045mol) polyester is (by hexanodioic acid, 1,6-hexylene glycol and neopentyl glycol make, molar average weight is 1700), this mixture was stirred 2 hours down at 85 ℃.No longer record NCO group by the IR spectrography this moment.After this mixture is cooled to 60 ℃, add 33.43g (0.375mol) dimethylethanolamine, stirred then 30 minutes.The deionized water that then adds 70 ℃ of 1369.3g stirred 60 minutes down at 60 ℃ then, stirred cooling down.Dispersions obtained have following character:

Solids content 42%

pH 8.26

Viscosity 210mPas

Particle diameter (laser correlation spectrometry, LCS) 70nm

Embodiment 16

(Bayer Corp Lai Wokusen) is dissolved in the 94.81g N-Methyl pyrrolidone with 85.72g Desmodur VL R 20 by stirring under the room temperature.Under 50 ℃, this homogenizing mixture dropwise to be mixed with the 56.50g methyl ethyl ketoxime, its speed makes and by thermopositive reaction the temperature of this batch of material to be risen to about 80 ℃.Under 80 ℃, it is stirred then, until no longer be measured to free NCO group (about 1 hour) by the IR spectrography.Add the solution of 28.77g dimethylol propionic acid in the 57.54g N-Methyl pyrrolidone down at 50 ℃ then, and 107.25g phenylbenzene methylene radical 4,4 '-vulcabond, stirred this mixture 1 hour.The nco value of this reaction mixture is 8.74% (calculated value: 9.31%).Add 446.72g (1.40eq OH) polyester (making) and 10.30g (0.078eq NCO) Desmodur VLR 20 (Bayer Corp then by hexanodioic acid, different phthalic acid, TriMethylolPropane(TMP), neopentyl glycol and propylene glycol, Lai Wokusen), stir this mixture until no longer record NCO group (3 hours) by the IR spectrography.Add the 19.12g dimethylethanolamine down at 50 ℃ then, stirred 20 minutes, be dispersed in the deionized water of 50 ℃ of 745.4g.Dispersions obtained have following character:

Solids content 45%

pH 7.93

Viscosity 1370mPas

Particle diameter (laser correlation spectrometry, LCS) 58nm

Embodiment 17

(Bayer Corp Lai Wokusen) is dissolved in 60.36g acetate methoxyl group propyl ester/butylacetate (1: 1, w/w) with 55.89g (0.414eq NCO) Desmodur VLR 20 by stirring under the room temperature.Through 30 minutes, dropwise add 36.07g (0.414eq) methyl ethyl ketoxime, temperature rises to 70 ℃ during this period.After 30 minutes, no longer record the NCO group through 70 ℃ of following restir by the IR spectrography.Add 30.18g (0.45eqOH) dimethylol propionic acid and 91.41g (0.822eq OH) isophorone diisocyanate then, reaction mixture was stirred 200 minutes down at 80 ℃; The NCO content of this moment is 5.69% (calculated value: 5.70%).Add 12.64g (0.036eq NCO) Desmodur Z 4470 (Bayer Corp, Lai Wokusen), 186.67g (0.585eqOH) polyester is (by hexanodioic acid, different phthalic acid, TriMethylolPropane(TMP), neopentyl glycol and propylene glycol make, the OH number is 189), 194.19g (0.492eq OH) polyester is (by different phthalic acid, hexanodioic acid, 1, the 6-hexylene glycol, TriMethylolPropane(TMP) and Tetra hydro Phthalic anhydride make, the OH number is 254), and 85.72g (0.0495eq) polyester is (by hexanodioic acid, 1,6-hexylene glycol and neopentyl glycol make, molar average weight is 1700), then this mixture was stirred 2 hours down at 85 ℃.No longer record NCO group by the IR spectrography this moment.After this mixture is cooled to 70 ℃, add 20.06g (0.225mol) dimethylethanolamine, stirred then 30 minutes.The deionized water that then adds 50 ℃ of 875.72g stirred 60 minutes down at 60 ℃, stirred down through cooling in 5 hours.Dispersions obtained have following character:

Solids content 42%

pH 8.43

Viscosity 5950mPas

Particle diameter (laser correlation spectrometry, LCS) 57nm

Embodiment 18

Repeat embodiment 17 described methods, but substitute the mixture of acetate methoxyl group propyl ester/butylacetate with 60.36g acetate methoxyl group propyl ester.Dispersions obtained have following character:

Solids content 42%

pH 8.2

Viscosity (Haake rotational viscosimeter, 23 ℃) 930mPas

Particle diameter (laser correlation spectrometry, LCS) 195nm

Following examples relate to carries out end-blocking to free isocyanate group in the reaction mixture.In this case, though find unexpectedly in fact also to have excessive hydroxyl except the end-capping reagent that adds, end capping obviously carries out very satisfactoryly.Required end-blocking speed is obviously fast a lot of compared with alcohol-isocyanate reaction, and thermodynamic reasoning is then indicated two kinds of all necessary generations of reactions under each situation.

Embodiment 19

50 ℃ are mixed 91.41g (0.41mol) isophorone diisocyanate by stirring down with the solution of 30.18g (0.225mol) dimethylol propionic acid in 60.36g acetate methoxyl group propyl ester, with this mixture heating up to 85 ℃, and stirred 3.5 hours down at 85 ℃.This moment, the NCO content of this reaction mixture was 8.55% (calculated value: 8.59%).Add 12.64g (0.036eq NCO) Desmodur Z 4470 then, 201.02g (0.63eqOH) polyester is (by hexanodioic acid, different phthalic acid, TriMethylolPropane(TMP), neopentyl glycol and propylene glycol make, the OH number is 189), 194.19g (0.492eq OH) polyester is (by different phthalic acid, hexanodioic acid, 1, the 6-hexylene glycol, TriMethylolPropane(TMP) and Tetra hydro Phthalic anhydride make, the OH number is 254), and 46.43g (0.054mol) polyester is (by hexanodioic acid, 1,6-hexylene glycol and neopentyl glycol make, molar average weight is 1700), this mixture was stirred 2 hours down at 85 ℃.No longer record NCO group by the IR spectrography this moment.After this mixture is cooled to 50 ℃, add 19.04g Shellsol SN 100,9.38g acetate methoxyl group propyl ester and 33.41g (0.384mol) methyl ethyl ketoxime, add 51.84g (0.384eq NCO) Desmodur VLR20 then, its adding speed makes temperature not exceed 60 ℃ (about 15 minutes).After 15 minutes, no longer record the NCO group by the IR spectrography.Then add 20.06g (0.225mol) dimethylethanolamine down, stirred the mixture 10 minutes, it is dispersed in the deionized water of 60 ℃ of 923.5g, stirred 60 minutes down in 60 ℃ again, stir down and in 4 hours, let alone cool to room temperature at 60 ℃.Dispersions obtained have following character:

Solids content 40%

pH 8.0

Viscosity 840mPas

Particle diameter (laser correlation spectrometry, LCS) 41nm

Embodiment 20

By stirring 91.41g (0.41mol) isophorone diisocyanate is mixed with 30.18g (0.225mol) dimethylol propionic acid and 60.36g acetate methoxyl group propyl ester down at 50 ℃, this mixture was stirred 2 hours down at 85 ℃; Its nco value is 8.06% (calculated value: 8.58%).Add 12.64g (0.036eq NCO) Desmodur Z 4470 then, 186.67g (0.585eq OH) polyester is (by hexanodioic acid, different phthalic acid, TriMethylolPropane(TMP), neopentyl glycol and propylene glycol make, the OH number is 189), 194.19 (0.492eq OH) polyester is (by different phthalic acid, hexanodioic acid, 1, the 6-hexylene glycol, TriMethylolPropane(TMP) and Tetra hydro Phthalic anhydride make, the OH number is 254), and 85.72g (0.099eq OH) polyester is (by hexanodioic acid, 1,6-hexylene glycol and neopentyl glycol make, molar average weight is 1700), this mixture was stirred 2 hours down at 85 ℃.No longer record NCO group by the IR spectrography this moment.After this mixture is cooled to 50 ℃, add 36.07g (0.414mol) methyl ethyl ketoxime, add 55.89g (0.414eq NCO) Desmodur VLR 20 then, its adding speed makes temperature be no more than 60 ℃ (about 15 minutes).Behind the restir 15 minutes, no longer record the NCO group by the IR spectrography.Then, carry out stirring in 10 minutes, this batch of material is dispersed in the deionized water of 60 ℃ of 875.72g, continue at 60 ℃ and stirred 60 minutes, stir following this batch of material cool to room temperature (4 hours) in 60 ℃ of adding 20.06g (0.225mol) dimethylethanolamines.This dispersion has following character:

Solids content 43%

pH 7.93

Viscosity (Haake rotational viscosimeter, 23 ℃) mPas

Particle diameter (laser correlation spectrometry, LCS) 52nm

Embodiment 21

Repeat embodiment 20 described methods, but with the butylacetate of 1: 1 (w/w) and the mixture replacing acetate methoxyl group propyl ester of acetate methoxyl group propyl ester.Dispersions obtained have following character:

Solids content 41%

pH 8.24

Viscosity (Haake rotational viscosimeter, 23 ℃) 3850mPas

Particle diameter (laser correlation spectrometry, LCS) 45nm

Embodiment 22

50 ℃ are mixed 100.55g (0.452mol) isophorone diisocyanate by stirring down with the solution of 33.20g (0.248mol) dimethylol propionic acid in 66.40g acetate methoxyl group propyl ester, with this mixture heating up to 85 ℃, and stirred 3.5 hours down at 85 ℃.This moment, the NCO content of this reaction mixture was 8.10% (calculated value: 8.58%).Adding 201.02g (0.63eq OH) polyester then (is made by hexanodioic acid, different phthalic acid, TriMethylolPropane(TMP), neopentyl glycol and propylene glycol, the OH number is 189), 194.19g (0.492eqOH) polyester is (by different phthalic acid, hexanodioic acid, 1,6-hexylene glycol, TriMethylolPropane(TMP) and Tetra hydro Phthalic anhydride make, the OH number is 254) and 46.43g (0.054eq OH) polyester (by hexanodioic acid, 1,6-hexylene glycol and neopentyl glycol make, molar average weight is 1700), this mixture was stirred 2 hours down at 85 ℃.No longer record NCO group by the IR spectrography this moment.After this mixture is cooled to 50 ℃, add 33.41g (0.384mol) methyl ethyl ketoxime, add 51.84g (0.384eq NCO) Desmodur VLR 20 then, its adding speed makes temperature be no more than 60 ℃ (about 15 minutes).Through after 15 minutes, no longer record the NCO group again by the IR spectrography.In 60 ℃ of adding 22.09g (0.248mol) dimethylethanolamines, stirred this mixture 10 minutes, and it is dispersed in the deionized water of 60 ℃ of 957.7g then, stirred 60 minutes down in 60 ℃ again, stir down and in 4 hours, let alone cool to room temperature.Dispersions obtained have following character:

Solids content 40%

pH 7.79

Viscosity (Haake rotational viscosimeter, 23 ℃) 230mPas

Particle diameter (laser correlation spectrometry, LCS) 44nm

Comparative Examples 1:

Repeat embodiment 7 described methods, but make all components (except the adding of embodiment 2 compounds) immediate response, promptly randomly (randomly) reacts according to WO 02/143395.Dispersions obtained have following character:

Solids content 23.7%

pH 7.93

Viscosity (Haake rotational viscosimeter, 23 ℃) pasty state therefore can't measured value

(the laser correlation spectrometry, LCS) pasty state therefore can't measured value for particle diameter

Therefore according to the description of Comparative Examples,, can not obtain stable dispersion even if having the solids content (be diluted to 23.7%, rather than 41% among the embodiment 7) of obvious reduction.The product of gained is a pasty state.

The performance characteristics of dispersion of the present invention is shown in Table 1.

Prepared Clear paint (Clearcoat material) with following composition.This Clear paint is used for the production of film, made this film at room temperature dry 10 minutes, then 140 ℃ or 160 ℃ of oven dry 30 minutes.Film to gained carries out Performance Testing.

Adopt Kang Nigefa (K

Nig method) measures pendulum hardness according to DIN 53157.

The contact all kinds of SOLVENTS was assessed solvability in 1 minute, and the order of solvent is as follows: dimethylbenzene/acetate methoxyl group propyl ester/ethyl acetate/acetone-

Assessment: 0, very good～5, poor.

Table 1

Obtain the embodiment No. of dispersion	7	8	9	10	11	12	13	15	16	19	20	21	22	Comparative Examples 1

Initial product weight [g]	150	150	150	150	150	150	150	150	150	150	150	150	150	150
															Additol XW 395 is as the form of supplying with [g]	1.1	1.2	1.1	1.2	1.1	1.1	1.2	1.1	1.2	1.1	0.3 ⁽⁴⁾	0.3 ⁽⁴⁾	0.3 ⁽⁴⁾	0.5
Surfynol 104,50%, in NMP [g]	1.1	1.2	1.1	-	1.1	1.1	1.2	1.1	1.2	1.1	-	-	-	0.5
															DMEA, 10%, Yu Shuizhong [g]	3.3	2.6	3.6	2.5	2.3	4.1	6.1	5.1	3.1	2.2	2.8	2.3	3.3	-
Distilled water [g]	21.0	26.0	6.0	12.0	20.5	44.0	27.3	6.0	16.0	14.0	18.0	22.5	13.0	-(2)
															Total amount [g]	176.5	181.1	161.7	165.7	175.0	200.3	185.8	163.4	174.7	168.3	175.1	175.1	166.6	151.0
Solid [%]	34.8	37.6	36.1	38.0	35.6	30	36	39	40.6	34.8	35.9	34.9	34.8	23.5
															Ejection time ISO 5mm[s]	39	40	41	38	40	41	40	39	38	36	39	40	38	112(2)
pH	8.3	8.4	8.3	8.3	8.4		8.4	8.3	8.3	8.3	8.3	8.4	8.3	7.8

Baking condition: 10 minutes RT+30 minute 140 ℃

Pendulum hardness [s]	232	36	97	191	149	230	200	90	221	98	74	81	102	(3)
															Solvability 1 minute (0-5)	2144	4455	4344	4344	4455	2244	2444	4444	1444	4444	4444	4444	3444	(3)
The outward appearance of film ⁽¹⁾	sat	sat.	sat.	sat.	sat.	sat.	sat.	sat.	sat.	sat.	sat.	sat.	sat.	(3)

Baking condition: 10 minutes RT+30 minute 160 ℃

Pendulum hardness [s]	229	39	111	196	163	231	220	104	232	108	84	94	114	(3)
															Solvability 1 minute (0-5)	1134	4444	4344	2244	4444	1134	2444	3444	1444	3444	3444	3444	3444	(3)
The outward appearance of film ⁽¹⁾	sat.	sat.	sat.	sat.	sat.	sat.	sat.	sat.	sat.	sat.	sat.	sat.	sat.	(3)

(1) sat.=is satisfied, zero defect; (2) because swelling property can't be regulated viscosity; (3) can't measure owing to the coalescent of film; (4) replace Additol XW 395 with Byk 347 (Byk chemical company, Byk Chemie, German Weser)

The required amount that the dispersion that makes with this method has aspect highly filled.In addition, the solvability of the shaping of film, cured film and pendulum hardness are all satisfactory.If do not adopt described method,, can not obtain the whole of these characteristics if change preparation unregulated polymer (random polymer) into.Therefore the structure of defined polymer architecture thing is very crucial for such coat system.The random method that can know from document can not produce described advantage (can not obtain the combination of described characteristic at least).

Claims

1. a method for preparing self-crosslinkable polyurethane dispersions makes a1 in the method) and a2) reaction obtain the NCO functional prepolymer, make this prepolymer and a3 then) and optional a4) reaction obtains OH official's energy and do not contain the urethane of NCO, wherein

A1) be polyisocyanates;

A2) be at least a polyol component, its average OH functionality 〉=2, number-average molecular weight is 62～2500g/mol, and also contains at least a hydroxyl functional carboxylic acid and/or sulfonic acid,

A3) be at least a other polyol component, its average OH functionality＞1, this polyol component comprises:

B1) binary～hexavalent alcohol, its number-average molecular weight are 62～300 g/mol,

B2) polyvalent alcohol, its OH functionality 〉=2, number-average molecular weight is 300～5000 g/mol, and/or

B3) simple function linear polyether, its number-average molecular weight are 300～3000 g/mol,

A4) be other polyisocyanate component, its can with a1) identical or different,

Component a1)～a4) complete reaction was carried out before or after adding blocked polyisocyanates, or at component a1)～a4) react after, make this blocked polyisocyanates by polyisocyanates and end-capping reagent in position, make a5 by adding neutralizing agent at last) deprotonation wholly or in part, and gained urethane is dispersed in the water, wherein

A5) be the acid groups of resulting composition.

2. the method for claim 1 is characterized in that, comprises that the isocyanate group of capping group and the ratio of all isocyanate-reactive groups are 0.8: 1～1.5: 1.

3. method as claimed in claim 1 or 2, it is characterized in that, at component a1) and/or a4) in adopted polyisocyanates or polyisocyanate mixtures based on following material: 1, hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI), ditan 2,4 '-and/or 4,4 '-vulcabond (MDI) and/or tolylene diisocyanate (TDI), dicyclohexyl methyl hydride 4,4 '-vulcabond.

4. method as claimed in claim 1 or 2; it is characterized in that, a1) and/or a4) in polyisocyanates comprise compound with following structure: urea diketone, carbodiimide, isocyanuric acid ester, iminooxadiazinedionepolyisocyanates diketone, biuret, carbamate, allophanate, oxadiazine triketone or acylurea.

5. method as claimed in claim 1 or 2 is characterized in that, described polyol component a2) average OH functionality be 2～6, number-average molecular weight is 62～500 g/mol, and contains at least a hydroxyl functional carboxylic acid and/or sulfonic acid.

6. method as claimed in claim 1 or 2 is characterized in that, a2) comprising: 1,4-butyleneglycol, 1,3 butylene glycol, 1,6-hexylene glycol, 2,2,4-trimethylammonium-1, polyester polyol and/or the polyether glycol of 3-pentanediol, TriMethylolPropane(TMP) and/or number-average molecular weight≤2000 g/mol.

7. method as claimed in claim 1 or 2 is characterized in that, wherein comprises hydroxypivalic acid and/or dimethylol propionic acid as acid-functionalized compound.

8. method as claimed in claim 1 or 2 is characterized in that, is used for components b 1) the number-average molecular weight of alcohol be 62～182 g/mol.

9. method as claimed in claim 1 or 2 is characterized in that, is used for components b 1) the number-average molecular weight of alcohol be 62～118 g/mol.

10. method as claimed in claim 1 or 2 is characterized in that, is used for components b 2) the number-average molecular weight of polyvalent alcohol be 300～3000 g/mol.

11. method as claimed in claim 1 or 2 is characterized in that, is used for components b 2) the number-average molecular weight of polyvalent alcohol be 300～2000 g/mol.

12. method as claimed in claim 1 or 2 is characterized in that, is used for components b 3) the number-average molecular weight of polyethers be 300～2000 g/mol.

13. method as claimed in claim 1 or 2 is characterized in that, is used for components b 3) the number-average molecular weight of polyethers be 300～1000 g/mol.

14. method as claimed in claim 1 or 2 is characterized in that, has also used catalyzer.

15. method as claimed in claim 1 or 2, it is characterized in that, adopt following material to neutralize: triethylamine, dianol, dimethylcyclohexylamine, trolamine, methyldiethanolamine, diisopropanolamine (DIPA), ethyl diisopropylamine, di-isopropyl hexahydroaniline, N-methylmorpholine, 2-amino-2-methyl-1-propanol, ammoniacal liquor or their any required mixtures.

16. a self-crosslinkable polyurethane dispersions, it obtains with each described method among the claim 1-15.

17. the purposes of the described self-crosslinkable polyurethane dispersions of claim 16 in preparation coating, tackiness agent and encapsulant.